International Journal Of Renewable Energy Research, IJRER

H.Erdener, A.Arinan, S.Orman, Vol.1, No.4, pp.252-258 ,2011

Future Fossil Fuel Alternative;

Di-methyl Ether (DME) A review

HulyaErdener‡, Ayca Arinan, Sultan Orman

* Tupras, Turkish Petroleum Refineries Corporation, Korfez 41790 Kocaeli/ TURKEY

‡ HulyaErdener; Address: Tupras, Turkish Petroleum Refineries Corporation, Korfez 41790 Kocaeli/ TURKEY,
e-mail: hulya.erdener@tupras.com.tr, ayca.arinan@tupras.com.tr, sultan.orman@tupras.com.tr

Received:11.07.2011 Accepted:12.09.2011

Abstract-The world energy consumption is steadily growing with the industrial improvements of the developing countries and
the readily available fossil fuel reserves lack in fulfilling this energy requirement. The depletion of the easily achievable
reserves; gives rise to the concept of oil production from oil shale and tar sands. However, the high cost and the operational
difficulties stand as the major drawback in front of these technologies. Along with these circumstances, and the environmental
concerns on fossil fuel consumption which is considered as the reasoning behind ‘Global warming’; world is seeking for
alternative fuel technologies. In this respect, this paper aims to give an insight on the allocation of ethers, mainly di-methyl
ether (DME), as fossil fuel alternatives. DME is considered as a possible candidate as LPG and diesel additive and/or substitute
due to the similarity between the physical properties and its high cetane number. Moreover, DME can be produced from a
variety of raw materials starting from biomass, coal and natural gas which results in production flexibility. This paper is a brief
review of the possible DME production processes, and the potential DME applications especially in transportation and
domestic utilizations.

Keywords-Di-methyl ether, alternative fuel, synthetic fuel, LPG, Diesel, fossil fuels.

1. Introduction for new, cheaper and sustainable solutions; or by

Energy is one of the principal concerns of the
industrialized world. There is a continuous growth
in the energy consumption with the industrial
improvements of the developing countries, which
results in higher amount of green house gas
emissions and elevated energy prices. Moreover,
natural gas and petroleum are important raw
materials for industry and their consumption rate
has increased more than 200 times in the last
century. Among them, petroleum is the one having
the fastest depletion rate because of its excessive
consumption for transportation. Its overuse for
transportation (about 57% of total oil
consumption) causes problems in the
petrochemical industry, in which petroleum is the
major raw material [1-2]. According to the
predicted lifetimes of precious raw materials, it is
expected that there will be significant fuel shortage
problems in the future. Thus, the world is looking
other means, alternative energy resources rather
than fossil fuels. The fuel alternative of the future
should have an easily available, non-petroleum
feedstock that enables production and fuel
versatility with reduced well to wheel green house
gas emissions and enhanced fuel performance.
Moreover, the infrastructure for fuel transportation
and storage must be well established. Among all
the alternative fuel candidates such as hydrogen,
methane, methanol, bio-fuels and Fischer Tropsch
fuels; ether based fuels, mainly di-methyl ether
(DME) takes a profound attention [3]. DME serves
as a clean, high efficiency compression ignition
fuel with low NOx and SOx emissions and reduced
particulate matter. It is an environmentally benign
fuel and does not possess large concerns with
toxicity, infrastructure, transportation and storage
as the other alternative fuel options [3].
International Journal Of Renewable Energy Research, IJRER
H.Erdener, A.Arinan, S.Orman, Vol.1, No.4, pp.252-258 ,2011

2. Di-methyl Ether (DME) DME is considered as a remarkable alternative

2.1. Characteristic Properties
Di-methyl ether is one of the most promising
non-petroleum fuel alternatives; which enables
high combustion performance with lower SOx,
NOx and CO2 emissions and sooth free operation.
It is the simplest form of all ethers with a chemical
formula of CH3OCH3. It is a liquefied gas under 6
atm (or -24.9°C @ 1 atm) pressure and possesses
similar properties with liquefied petroleum gas,
LPG; thus it can be handled with an infrastructure
similar to LPG [3, 4]. Upon burning DME displays
a visible blue flame like natural gas which is a
crucial safety indicator and it does not require an
odorant since it has an ether-like scent [4].
Characteristic properties of DME and its
comparison with other commonly utilized fuels are
given in Table 1.
2.2. Advantages of DME as a fuel
Table 1. Comparison of characteristic properties of DME with some commonly used fuels [5]
DME Methane Methanol
for diesel and LPG with sooth free operation and
enhanced engine efficiency. The low auto-ignition
temperature of DME and its quick vaporisation
upon injection into the engine cylinder results in
high cetane number (~55-60), hence improves the
engine performance. Moreover, the high oxygen
content (~35% wt) and the absence of carbon-
carbon bonds lead to enhanced combustion
kinetics, smokeless combustion, low amount of
particulate matter [8, 9]. Moreover, DME is non-
carcinogenic, non-teratogenic, non-mutagenic, and
non-toxic [3].
By utilization of DME in light and heavy duty
vehicles, well to wheel energy efficiency is
expected to be 19% and 22.5% respectively,
whereas the highest energy efficiency is around
26% for direct injection diesel vehicles [10]. With
proper modifications on the engine injection and
combustion systems, the NOx emissions will reach
the ultra low emission limits (ULEV).
Ethanol FTD LPG Gasoline Diesel Hydrogen

Molecular Weight (g mol-1) 46.07 16.04 32.04 46.07 44.1 114 198.4 2.016

Density (g cm-3) 0.67c 0.00072b 0.792b 0.785b 0.76-0.79e 0.54 e 0.71-0.77 e 0.80-0.86b 0.00089 e

Normal boiling point (˚C) -24.9 -162 64 78 180-320 e -30 e 0-210 e 125-400 -253 e

Octane Number (RON) - 122 110 110 - 90-96 90-100 - >125

Cetane Number 55-60 - 5 - 55-75 - - 40-55 -

Energy content e (MJ/kg) 28,43 50 19.5 28,4 44 46.3 42.7 43.1 119.9

Carbon Content f (wt%) 52.2 74 37.5 52.2 85 e 82 e 85.5 87 0

Sulfur Content f (ppmg) 0 ~7-25 0 0 10-50 ~200 ~250 0

a Fischer Tropsch Diesel In addition, well to wheel carbon dioxide

bValues per cm3 of vapour at standard
temperature and pressure [3]
c Density at P=1 atm and T= 20˚C
d Data reproduced from reference [6]
e Data reproduced from reference [6]
f Data reproduced from reference [7]
g Mass basis
emissions are comparable with direct injection
diesel engines [4].
2.3. Disadvantages of DME utilization
DME has a lower combustion enthalpy
compared to petroleum based fuels due to the high
oxygen content. For this reason, in order to achieve
the same combustion performance, a larger volume
of fuel should be injected into the engine cylinder,
thus a longer injection time and larger fuel storage
tank is required.

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H.Erdener, A.Arinan, S.Orman, Vol.1, No.4, pp.252-258 ,2011
The low viscosity of DME (~0.1cSt), will lead to
leakage problems from the fuel supply systems;
thus special attention must be given for sealing [5].
Moreover, due to its corrosive nature, DME is not
compatible with most of the elastomers. In order to
prevent the deterioration after long exposure times,
seals can be made from polytetrafluoroethylene
(PTFE) based materials [4].
Another consequence of low viscosity reveals
itself as the lower lubricity characteristics of DME
[4]. Lower lubricity may cause extensive wear on
the moving parts of the engine. This problem can
be overcome by the introduction of some
lubricants.
3. Production Processes
3.1. In-direct Synthesis (Conventional route)
Conventionally, DME is produced via two-step
process, in which synthesis gas (syngas) is first
converted to methanol, followed by the
dehydration of methanol over an acidic catalyst
[11] in order to form DME. Methanol dehydration
reaction occurs easily over almost any dehydration
catalyst at relatively low temperature ranges
between 250-300°C in vapor phase and the
reaction is pressure insensitive [12]. Syngas
provides a versatile feedstock. It can be produced
either by gasification of various bio-mass sources,
coal or waste material or by reformation of natural
gas with steam. The latter feedstock is usually
preferred since it does not contain impurities such
as sulphur components and heavy metals. The
reactions involved in two-step production process
are as follows [3, 4, 11];
Methanol Synthesis;
CO+ 2H2→CH3OH, ΔH˚rxn=-90.3 kJ mol-1
CO2+ 3H2→CH3OH+ H2O, ΔH˚rxn=-49.4 kJ mol
(2)
Methanol Dehydration;
2CH3OH→CH3OCH3 +H2O, ΔH˚rxn = -23.4 kJ
mol-1 (3)
Water-gas shift;
H2O+ CO →CO2 +H2, ΔH˚rxn = -40.9 kJ mol-1(4)
Net Reaction;
3H2+ 3CO →CH3OCH3 +CO2, ΔH˚rxn = -258.6 kJ
mol-1 (5)
3.2. Direct Synthesis
Recently, a new system is proposed, at which,
methanol synthesis and dehydration processes are
combined in the same reactor for DME synthesis
[13]. This method is referred as direct synthesis
and is economically favourable since the cost of
methanol separation and its preparation as a
feedstock for DME synthesis reactor is avoided
[11]. Additionally, the thermodynamic limitations
of methanol synthesis could be withdrawn, since
consumption of methanol in a consequent reaction
to form DME will shift the methanol synthesis
equilibrium towards higher methanol conversion
[14, 15].
In direct synthesis, initially, the feedstock (bio-
mass, coal or natural gas, etc.) is converted into
syngas. Later, methanol is synthesised from syngas
(given in eq.1, eq.2) and converted into DME via
methanol dehydration reaction (given in eq.3)
simultaneously in one step over catalysts having
two active sites.
In direct synthesis of DME, a wide range of feed
composition and operating conditions can be used.
Feed gas composition, source of feed gas and
catalyst selections are the important parameters of
the process [12]. Typical reaction conditions of
direct DME synthesis are tabulated in Table 2.
[16].
Table 2. Reaction conditions of direct DME synthesis [16]
Reaction Conditions Range
Temperature (°C) 240-280
Pressure (bar) 30-80
(1)
Feed (H2 / CO) ratio 0.5-2.0
-1
Catalyst loading ratio (W/F) 3.0-8.0
[kg-cat.*h/kg-mol]
The overall reaction is highly exothermic, thus
the temperature control in the reactor is crucial to
prevent run-away reactions [11]. In commercial
applications, two different reactor types are
utilized; fixed bed [17] and slurry phase [18].
Temperature control is difficult in fixed-bed
reactor, since hot spots may occur during the
process. The slurry phase reactor will overcome
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H.Erdener, A.Arinan, S.Orman, Vol.1, No.4, pp.252-258 ,2011
this problem, thus, they will achieve better
temperature control. In slurry phase reactors, the
catalyst particles are suspended in an oil solvent;
which ease the temperature control due to large
heat capacity of the solvent [11]. These types of
reactors are preferred in pilot and commercial
scales. Moreover, thermally coupled heat
exchanger reactor, micro-channel reactor and
catalytic distillation reactors are of interest and
being developed in laboratory scale.
4. Application Areas
In 1990s, the worldwide DME production was
around 100,000-150,000 tonnes per annum [19]
and was mainly used in aerosol industry as a
propellant in the spray cans. In the recent years,
DME has received a growing attention due to its
potential as a fuel additive and/or alternative.
Thus, DME covers a wide application area ranging
from domestic and industrial utilizations to
transport applications.
4.1. Domestic Utilizationi
DME possesses similar properties to butane and
propane; which is a potential substitute for LPG
[20, 21] and can be utilized for household cooking
applications. DME can be blended with LPG up to
20% by weight and will be transported by the
existing LPG infrastructure without any
modifications. Along with these circumstances, the
low greenhouse gas emissions and particulate
matter emissions attracts a substantial interest on
DME as a cooking fuel. Especially in China, there
is a considerable potential for coal derived DME
[19].
4.2. Industrial Utilization
DME was formerly used as a medical
anaesthetic [19] and has found a large application
area as an injection agent for sprays for paint,
agricultural chemicals and cosmetics [23] in order
to replace chlorofluorocarbons (CFC’s) which
have undesired effects on the ozone layer.
Furthermore, DME can go through a phase change
from liquid to gas easily, thus can be considered as
a good refrigerant [18].
Moreover, DME provides an excellent potential
as a feedstock in the production of several
important chemicals such as olefins. DME
possesses a lower enthalpy value compared to
methanol, thus, the heat of reaction required for the
production of a chemical will be much lower when
DME is utilized instead of methanol [5].
4.3. As a Fuel Alternative
DME is an attractive fuel alternative for
compression ignition engines. Besides its high
cetane number, DME can easily vaporize during
injection allowing lower fuel injection
pressuresdue to its low boiling point. The required
fuel injection pressure of DME is around 220 atm
at full loading, whereas the diesel engines required
injection pressures higher than 1200 atm [5]. The
existing diesel engines can be compatible with
DME subsequent to some modifications that are
required to maintain stable fuel injection to the
engine [5]. Similar to the other alternative fuels,
DME also has a lower energy density per unit
volume compared to diesel. Thus, in order to travel
the same distance, a larger storage tank must be
provided on the vehicle [5, 22].
Moreover, DME is considered as a possible LPG
alternative and/or substitute. It can be utilized on
LPG compatible vehicles up to 20wt% blending
ratio without any modifications on the engine
ignition system or LPG infrastructure. For higher
blending ratios or direct DME injection,
modifications are required as for diesel.
4.3.1. Performance criteria
Evaluation of DME as an alternate to
conventional fuels can be performed via
comparison in terms of well to tank efficiencies. In
Figure 1, the fuel properties of DME are compared
with other fuels [3]
Considering the abundance and improvements
on processing technology, petroleum based fuels
owe the highest WTT efficiencies approaching up
to 90% and is well above DME efficiency which is
around 70%. However, it is shown that, DME
fuelled compression-ignition engines has a higher
thermal efficiency compared to diesel due to its
structure and promising fuel properties as shown in
Figure 2.
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H.Erdener, A.Arinan, S.Orman, Vol.1, No.4, pp.252-258 ,2011

Fig.1. Well to tank (WTT) efficiencies of fuels [3]

Fig.2. Thermal efficiency of DME and diesel fuelled engines

[24]
(a)
4.3.2. Emissions
DME utilization in compression engine,
compared with conventional diesel and other fuels,
is reported as advantageous in terms of pollutant
emissions as well. In relation with the improved
thermal efficiency behaviour as mentioned in
previous section, emitted hydrocarbon, NOx and
CO amounts are reduced in presence of DME in
the engine. In Figure 3, emissions of NOx and CO
in DME fuelled engine is compared with gas-to-
liquid (GTL) and diesel fuelled engines under a
load of 1400 rpm [25].
(b)
Fig. 3. (a) CO and (b) NOx emissions with diesel, GTL and
DME fuelled engines at 1400 rpm load [25]

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H.Erdener, A.Arinan, S.Orman, Vol.1, No.4, pp.252-258 ,2011
5. Conclusion
DME is a promising new alternative fuel with its
versatile feedstock and production methods. It
finds a wide application area ranging from
household and industrial applications to
transportation. Especially, considered as a multi-
purpose fuel and suggested as a LPG/diesel
additive (with a maximum blend ratio of 20% for
LPG) and/or substitute [26]. DME shows a good
performance in conventional diesel engines with
modified injection and storage systems due to its
high cetane number. It provides a quiet combustion
and clean burning and prevents sooth formation.
DME finds a primary market especially as an
injection agent in aerosols and as chemical
feedstock; and there is a continuously developing
market for DME as an alternative fuel that is led
by China, Japan and Europe. In order to use DME
in daily life, as it is competitive with its promising
fuel properties, the production routes should also
be optimized in terms of costs to find a place in
economy. Since natural gas prices are affected by
several items and it is the main feedstock of DME
production beside coal and biomass, DME unit
costs are not stable as well.
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